Phthalocyanine compounds

ABSTRACT

A compound of formula (1) and salts thereof, wherein: M is a metal or hydrogen; Pc is a phthalocyanine nucleus; each R 1  independently is H or optionally substituted alkyl aryl or aralkyl; each L 1  independently is a divalent organic linking group; Z is an optionally substituted piperazinyl group; q is 1 or 2; x and y each independently have a value of 0.5 to 3.5; and (x+y) is from 2 to 5. A process for making the compounds of formula (1). The compounds of formula (1) are useful as colorants for inks which are used in for example ink jet printing of substrates such as paper, plastics, textile materials, metal or glass.

This application is a 371 of PCT/GB95/02300 filed Sep. 20, 1996.

This invention relates to phthalocyanine compounds, a process for makingsuch compounds, inks containing the compounds and processes for printingthe inks especially by ink jet printing and substrates when printed withthe inks.

Ink jet printing is a non-impact printing technique which involvesejecting, thermally or by action of an oscillating piezo crystal,droplets of ink continuously or on demand from a fine nozzle directlyonto a substrate such as paper, plastics, textile, metal or glass. Theink may be aqueous, solvent or hot melt based and must provide sharp,non-feathered images which have good water fastness, light fastness andoptical density, have fast fixation to the substrate and cause noclogging of the nozzle.

According to the present invention there is provided a compound ofFormula (1) and salts thereof: ##STR2## wherein: M is a metal orhydrogen;

Pc is a phthalocyanine nucleus;

each R¹ independently is H or optionally substituted alkyl aryl oraralkyl;

each L¹ independently is a divalent organic linking group;

Z is an optionally substituted piperazinyl group;

q is 1 or 2;

x and y each independently have a value of 0.5 to 3.5; and

(x+y) is from 2 to 5.

M is preferably copper, nickel, scandium, titianium, vandium, chromium,manganese, iron, cobalt, zinc, lithium, sodium, potassium, magnesium,calcium, barium, aluminium, silicon, tin, lead or rhodium, morepreferably copper, nickel, scandium, titanium, vanadium, chromium,manganese, iron, cobalt or zinc, especially copper or nickel and moreespecially copper. When M is tri- or tetra-valent the valencies above 2may be taken by coordination with halogen atoms or oxygen e.g. VO, AlCl,PbCl₂.

Each R¹ independently is preferably H; optionally substituted C₁₋₄-alkyl, especially C₁₋₄ -alkyl; optionally substituted phenyl; C₇₋₁₁-aralkyl, especially benzyl. It is particularly preferred that R¹ is H.

The divalent organic linking group represented by L¹ is preferablyalkylene, especially C₁₋₆ -alkylene, more especially C₂₋₄ -alkylene;aralkylene, preferably C₇₋₁₁ -aralkylene, especially phenyl-C₁₋₄-alkylene; or arylene, preferably arylene having up to ten carbon atoms,especially, phenylene; which may be substituted or unsubstituted.

As examples of alkylene and aralkylene groups represented by L¹, theremay be mentioned:

ethylene

1,2- and 1,3-propylene

2-hydroxy-1,3-propylene

1- and 2-phenyl-1,3-propylene

2-(4'-sulphophenyl)-1,3-propylene

1,4-, 2,3- and 2,4-butylene

2-methyl-1,3-propylene

2-methyl-2,4-pentylene

2,2-dimethyl-1,3-propylene

1-phenylethylene

1-chloro-2,3-propylene

1,6- and 1,5-hexylene

2,3-diphenyl-1,4-butylene

1-(methoxycarbonyl)-1,5-pentylene

1-carboxy-1,5-pentylene

2,7-heptylene

3-methyl-1,6-hexylene

--CH₂ CH₂ OCH₂ CH₂ --

--CH₂ CH₂ SCH₂ CH₂ --

--CH₂ CH₂ SSCH₂ CH₂ -- ##STR3##

As examples of arylene radicals represented by L¹ there may be mentioned1,2-, 1,3- and 1,4-phenylene and 1,4-naphthylene which are optionallysulphonated.

It is preferred that the divalent linking group L¹ is an optionallysubstituted C₂ -C₆ alkylene linking group, especially a group of theFormula --C_(n) H_(2n) -- wherein n is 2 to 6, preferably 2 to 4, morepreferably 2.

The optional substituents which may be present on the piperazinyl groupT are preferably selected from optionally substituted alkyl, aryl,aralkyl, aryl ester and H.

When substituted, the piperazinyl group Z may contain up to 5substituents, preferably up to 3. The substituents may be at the 2-, 3-,4-, 5- or 6-positions of the piperazinyl group Z, especially at one ormore of the 3-, 4- and 5-positions.

Accordingly, Z is preferably of Formula (2): ##STR4## wherein: R² and R³each independently is H or optionally substituted alkyl; and

R⁴ is H, optionally substituted alkyl, aryl, aralkyl, acyl or an estergroup.

R² and R³ are preferably H or optionally substituted C₁₋₄ -alkyl, morepreferably H or CH₃, especially H.

R⁴ is preferably H, optionally substituted C₁₋₄ -alkyl or optionallysubstituted phenyl, especially an optionally substituted C₁₋₄ -alkylgroup. Preferred ester and acyl groups are of the Formula --CO₂ W and--COW respectively wherein W is optionally substituted aryl oroptionally substituted alkyl, especially C₁₋₄ alkyl, phenyl or benzyl.

When R⁴ is an optionally substituted alkyl group, it is preferably ofFormula (3): ##STR5## wherein: L¹ and each R¹ independently are ashereinbefore defined.

It is preferred that the divalent organic linking group L¹ in R⁴ isoptionally substituted C₂₋₆ -alkylene, more preferably a group ofFormula --C_(n) H_(2n) --, especially --(CH₂)_(n) --, wherein n is ashereinbefore defined.

When R¹, R², R³, R⁴, W or the divalent linking group L¹ is optionallysubstituted it is preferred that the substituents are selected from C₁₋₄alkyl, especially methyl; C₁₋₄ -alkoxy, especially methoxy; carboxy;sulpho; amino, especially NH₂ ; halo; --CN; and NO₂.

The sum of (x+y) is preferably from 3 to 4, more preferably 4. It ispreferred that x is from 1.5 to 3.0. Preferred values of y are from 1.0to 2.5. As will be appreciated the value of (x+y) is an average valueand the definition provided for the invention includes single compoundsand compositions. Preferably q is 2.

The present invention includes not only compounds of Formula (1) butalso mixtures of compounds of Formula (1) and salts thereof. Preferredsalts are those with alkali metals, especially Na, Li and K; orsubstituted ammonium.

The substituted ammonium cation may be a quaternary ammonium group ofthe Formula ⁺ NQ₄ in which each Q independently is an organic radical,or two or three Qs together with the nitrogen atom to which they areattached form a heterocyclic ring and all remaining Qs are selected fromC₁₋₄ -alkyl. Preferred organic radicals represented by Q are C₁₋₄ -alkylradicals, especially methyl radicals. Preferred heterocyclic ringsformed by NQ₄ are 5 or 6 membered heterocyclic rings such as pyridinium,piperidinium and morpholinium.

As examples of quaternary ammonium groups of Formula ⁺ NQ₄ there may bementioned N⁺ (CH₃)₄, N⁺ (CH₂ CH₃)₄, N-methyl pyridinium, N,N-dimethylpiperidinium and N,N-dimethyl morpholinium. Alternatively thesubstituted ammonium cation may be a group of Formula ⁺ NHT₃ whereineach T independently is H or C₁₋₄ -alkyl, or two or three groupsrepresented by T together with the nitrogen atom to which they areattached form a 5 or 6 membered ring, especially a pyridinium,piperidinium or morpholinium ring.

As examples of groups of Formula ⁺ NHT₃ there may be mentioned (CH₃)₃ N⁺H, (CH₃)₂ N⁺ H₂, H₂ N⁺ (CH₃)(CH₂ CH₃), CH₃ N⁺ H. CH₃ CH₂ N⁺ H₃, H₂ N⁺(CH₂ CH₃)₂, CH₃ CH₂ CH₂ N⁺ H₃, ⁺ NH₄, (CH₃)₂ CHN⁺ H₃, pyridinium,piperidinium and morpholinium.

A particularly preferred compound of Formula (1) is of Formula (4) andsalts thereof: ##STR6## wherein: M, Pc,R¹, R², R³ and R⁴ are ashereinbefore defined;

R⁵ is H or optionally substituted alkyl;

L² and L³ each independently is an optionally substituted alkylenelinking group;

(x+y) is from 3 to 4;

y is from 1 to 2.5; and

b is 0 or 1.

In the compounds of Formula (4) it is preferred that R¹ is H, R⁵ ispreferably H or optionally substituted C₁₋₄ alkyl, more preferably, L²and L³ each independently is preferably an optionally substitutedalkylene linking group as hereinbefore defined for L¹, especially C₂₋₄-alkylene.

The groups R² and R³ are preferably at the 2- and 5-positions on thepiperazinyl ring.

According to a further aspect of the present invention there is provideda process for the preparation of a compound of Formula (1) comprisingcondensing a compound of Formula (5) and a compound of Formula (6):##STR7## wherein M, Pc, R¹, L¹, x, y and Z are as hereinbefore definedand G is a labile atom or group.

Preferred labile atoms represented by G are halogens, especially Cl andBr and a preferred labile group represented by G is OSO₃ H.

The condensation is preferably performed in the presence of base. Thebase may be any inorganic or organic base such as an alkali metal oralkali earth metal hydroxide, carbonate or bicarbonate or an organicbase. Preferred organic bases are tertiary amines such as N-alkylatedheterocycles, for example N-(C₁₋₄ -alkyl)morpholine, N-(C₁₋₄ -alkyl)piperidine, and N,N-di(C₁₋₄ -alkyl) piperazine: tri (C₁₋₄ -alkyl)amines,for example triethylamine; and optionally substituted pyridine,especially unsubstituted pyridine.

The amount of base used may be varied between wide limits but it ispreferred to use less than 40, more preferably less than 10 andespecially from 3 to 5 moles of base for each mole of the compound ofFormula (5).

The condensation is preferably performed using water as solvent. Ambienttemperatures may be employed in conjunction with a reaction time of, forexample, 5-24 hours, or elevated temperatures of from 30° C. to 150° C.,preferably from 50° C. to 100° C., can be used for a shorter period.

After the condensation the product may be isolated by acidifying thereaction, mixture, preferably using a mineral acid, especiallyhydrochloric acid. Where the product precipitates as a solid it may beseparated from the mixture by filtration.

If desired unwanted anions may be removed from the product of the aboveprocess by dialysis, reverse osmosis, ultrafiltration or a combinationthereof.

The product of the above process may be converted, where necessary, tothe alkali metal, NH₄ ⁺, quaternary ammonium or organic amine salt bythe addition of an alkali metal hydroxide, ammonia, ammonium hydroxide,primary, secondary, tertiary or quaternary amine. When the base used inthe condensation process is an organic amine an excess of the organicamine may be used so that sulpho groups in the compound of Formula (1)are converted into their organic amine salt in situ.

When the compound of Formula (6) has two amino groups, the abovedescribed process can give a mixture of compounds of Formula (1)depending on which of the amino groups displaces the labile group G inthe compound of Formula (5). For example, N-(2-aminoethyl) piperazinehas an --NH₂ and an --NH-- group, either of which can react with thecompound of Formula (5). Thus the mixture results in which some of thecompound of Formula (5) has reacted with the --NH₂ group and some hasreacted with the --NH-- group of the N-(2-aminoethyl)piperazine.

The compound of Formula (5) may be prepared by condensing a compound ofFormula MPc(SO₂ Cl).sub.(x+y) with an amine of Formula HNR¹ --L¹ --Gwherein M, Pc, x, y, R¹, L¹ and G are as hereinbefore defined. Thiscondensation is preferably performed under aqueous conditions such asthose described above for preparation of the compound of Formula (1).

The abovementioned compound of Formula MPc (SO₂ Cl)_(x+y) may beprepared using known methods, for example by heating a metal-free ormetal-containing phthalocyanine optionally having three or four sulphogroups with chlorosulphonic acid, optionally followed by heating withPCl₃. Typically the heating with chlorosulphonic acid is performed above60° C., preferably above 100° C., especially in the range 120° C. to165° C., preferably over a period of from 1 to 24 hours. Heating withPCl₃ is preferably performed at a lower temperature, especially 80-105°C., over a period of 10 to 48, preferably 10 to 30 hours.

Examples of compounds of Formula HNR¹ --L¹ --G which may be used in theabove process include 2-chloroethylamine, 3-chloropropylamine,4-chloromethyl-benzylamine, 2-bromoethylamine and 3-bromopropylamine.

Examples of compounds of Formula (6) which may be used in the aboveprocess include 1-(2-aminoethyl)-piperazine, piperazine,1-(2-hydroxyethyl) piperazine, 1-methylpiperazine, 1,4-bis(3-aminopropyl)piperazine, 1-(3-aminopropyl)-4-methylpiperazine,1-(2-hydroxyethoxyethyl)piperazine, 2-methylpiperazine and1-(carboxymethyl)piperazine.

The product of the above process forms a further feature of the presentinvention.

The compounds of Formula (1) are especially useful for the preparationof inks and accordingly there is provided an ink comprising a compoundof Formula (1) or a salt thereof and a medium. The inks are used in inkjet printing and particularly thermal ink jet printing. The inks can beprepared according to known formulations. The compounds of Formula (1)have high water fastness when printed onto paper, even when in the formof a salt with a metal (e.g. Na, K). Thus it is preferred to use freeacids or metal salts of the compounds of Formula (1) rather than thepotentially unpleasantly odorous amine salts to achieve good fastnessresults.

A preferred ink comprises a compound of Formula (1) and a liquid medium,preferably an aqueous medium. It is preferred that the compound iscompletely dissolved in the liquid medium to form a solution.

The ink preferably contains from 0.5% to 20%, more preferably from 0.5%to 15%, and especially from 1% to 5%, by weight of the compound ofFormula (1), based on the total weight of the ink. Although the ink maycontain less than 5% by weight of the compound of Formula (1) it isdesirable that the dye has a solubility of around 10% or more to allowthe preparation of concentrates which may be used to prepare more diluteinks and to minimise the chance of precipitation of the compound ofFormula (1) if evaporation of the medium occurs during use.

The liquid medium, is preferably water or a mixture comprising water anda water-soluble organic solvent, preferably in a weight ratio from 99:1to 1:99, more preferably from 95:1 to 50:50 and especially from 90:10 to60:40.

The water-soluble organic solvent is preferably a C₁₋₄ -alkanol such asmethanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol or isobutanol; an amide such as diemthylformamide ordimethylacetamide; a ketone or ketone alcohol such as acetone ordiacetone alcohol; an ether such as tetrahydrofuran or dioxane; apolyalkylene glycol such as polyethylene glycol or polypropylene glycol;an alkylene glycol or thioglycol containing a C₂ -C₆ alkylene group suchas ethylene glycol, propylene glycol, butylene glycol or triethyleneglycol; a thiodiglycol, hexylene glycol, or diethylene glycol; a polyolsuch as glycerol or 1,2,6-hexanetriol; a lower alkyl ether of apolyhydric alcohol such as 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol,2-[2-(methoxyethoxy)ethoxy]ethanol,2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-pyrrolidone or N-methylpyrrolidone; or a mixture containing two ormore of the aforementioned water-soluble organic solvents.

Preferred water-soluble organic solvents are selected from2-pyrrolidone, N-methylpyrrolidone, an alkylene glycol or lower alkylether of a polyhydric alcohol such as ethylene glycol, diethyleneglycol, triethylene glycol or 2-methoxy-2-ethoxy-2-ethoxyethanol; and apolyethylene glycol with a molecular weight of up to 5000. A preferredspecific solvent mixture is a binary mixture of water and eitherdiethylene glycol, 2-pyrrolidone or N-methylpyrrolidone in a weightratio as mentioned above.

Example of suitable ink media are given in U.S. Pat. Nos. 4,963,189,4,703,113, 4,626,284 and EP 4,251,50A.

It is preferred that the inks of the present invention further compriseone or more of a penetrant to assist permeation of the dye into a papersubstrate and a buffer such as sodium borate, to stabilise the pH of theink.

A further aspect of the present invention provides a process forprinting a substrate with an ink using an ink jet printer. characterisedin that the ink contains at least one compound of Formula (1) or saltthereof.

A suitable process for the application of an ink as hereinbefore definedcomprises forming the ink into small droplets by ejection from areservoir through a small orifice so that the droplets of ink aredirected at a substrate. This process is commonly referred to as ink jetprinting, and the ink jet printing processes for the present inks arepreferably piezoelectric ink jet printing, and more especially thermalink jet printing. In thermal ink jet printing, programmed pulses of heatare applied to the ink by means of a resistor, adjacent to the orificeduring relative movement between the substrate and the reservoir.

Substrates may be paper, plastics, textiles, metal or glass. Preferredsubstrates are overhead projector slides or cellulosic substrates,especially plain paper, which may have an acid alkaline or neutralcharacter.

The preferred ink used in the process is as hereinbefore described.

According to a still further aspect of the present invention there isprovided a paper or an overhead projector slide printed with a compoundof Formula (1) or salt thereof.

According to a further aspect of the present invention there is provideda process for the coloration of a textile material with any of theabovementioned ink compositions comprising a compound of Formula (1)which comprises the steps:

i) applying to the textile material by ink jet printing the inkcomposition; and

ii) heating the textile material at a temperature from 50° C. to 250° C.to fix the dye on the material.

The process for coloration of a textile material by ink jet printingpreferably comprises a pre-treatment of the textile material with anaqueous pre-treatment composition comprising a water-soluble base, ahydrotropic agent and a thickening agent followed by removing water fromthe pre-treated textile material to give a dry pre-treated textilematerial which is subjected to ink jet printing in step i) above.

The pre-treatment composition preferably comprises a solution of thebase and the hydrotropic agent in water containing the thickening agent.

The base is preferably an inorganic alkaline base, especially a salt ofan alkali metal with a weak acid such as an alkali metal carbonate,bicarbonate or silicate or an alkali metal hydroxide. The amount of basemay be varied within wide limits provided sufficient base is retained onthe textile material after pre-treatment to promote the dyeing of thepre-treated textile material. Where the base is sodium bicarbonate it isconvenient to use a concentration of from 1% to 5% by weight based onthe total weight of the composition.

The hydrotropic agent is present to provide sufficient water to promotethe fixation reaction between the dye and the textile material duringthe heat treatment, in step (d) above, and any suitable hydrotropicagent may be employed. Preferred hydrotropic agents are urea, thioureaand dicyandiamide. The amount of hydrotropic agent depends to someextent on the type of heat treatment. If steam is used for the heattreatment generally less hydrotropic agent is required than if the heattreatment is dry, because the steam provides a humid environment. Theamount of hydrotropic agent required is generally from 2.5% to 50% byweight of the total composition with from 2.5% to 10% being moresuitable for a steam heat treatment and from 20% to 40% being moresuitable for a dry heat treatment.

The thickening agent may be any thickening agent suitable for use in thepreparation of print pastes for the conventional printing of cellulosereactive dyes. Suitable thickening agents include alginates, especiallysodium alginate, xanthan gums, monogalactam thickeners and cellulosicthickeners. The amount of the thickening agent can vary within widelimits depending on the relationship between concentration andviscosity. However, sufficient agent is preferred to give a viscosityfrom 10 to 1000 mPa.s, preferably from 10 to 100 mPa.s, (measured on aBrookfield RVF Viscometer). For an alginate thickener this range can beprovided by using from 10% to 20% by weight based on the total weight ofthe pre-treatment composition.

The remainder of the pre-treatment composition is preferably water, butother ingredients may be added to aid fixation of the dye to the textilematerial or to enhance the clarity of print by inhibiting the diffusion(migration) of dye from coloured areas to non-coloured areas beforefixation.

Examples of fixation enhancing agents are cationic polymers, such as a50% aqueous solution of a dicyanamide/phenol formaldehyde/ammoniumchloride condensate e.g. MATEXIL FC-PN (available from ICI), which havea strong affinity for the textile material and the dye and thus increasethe fixation of the dye on the textile material.

Examples of anti-migration agents are low molecular weight acrylicresins, e.g. polyacrylates, such as poly(acrylic acid) and poly(vinylacrylate).

In the pre-treatment stage of the present process the pre-treatmentcomposition is preferably evenly applied to the textile material. Wherea deeply penetrated print or a deep shade is required the pre-treatmentcomposition is preferably applied by a padding or similar process sothat it is evenly distributed throughout the material. However, whereonly a superficial print is required the pre-treatment composition canbe applied to the surface of the textile material by a printingprocedure, such as screen or roller printing, ink jet printing or barapplication.

In the pre-treatment stage of the present process, water may be removedfrom the pre-treated textile material by any suitable drying proceduresuch as by exposure to hot air or direct heating, e.g. by infra-redradiation, or micro-wave radiation, preferably so that the temperatureof the material does not exceed 100° C.

The application of the ink composition to the textile material, stage(i) of the present process, may be effected by any ink jet printingtechnique, whether drop on demand (DOD) or continuous flow. The inkcomposition, preferably also contains a humectant to inhibit evaporationof water and a preservative to inhibit the growth of fungi, bacteriaand/or algae in the solution. Examples of suitable humectants are,propan-1,2-diol, butan-1,2-diol, butan-2,3-diol and butan-1,3-diol.However, the presence of small amounts, up to about 10%, preferably notmore than 5%, in total, of polyols having two or more primary hydroxyand/or primary alcohols is acceptable, although the composition ispreferably free from such compounds. Where the ink jet printingtechnique involves the charging and electrically-controlled deflectionof drops the composition preferably also contains a conducting materialsuch as an ionised salt to enhance and stabilise the charge applied tothe drops. Suitable salts for this purpose are alkali metal salts ofmineral acids.

After application of the ink composition, it is generally desirable toremove water from the printed textile material at relatively lowtemperatures (<100° C.) prior to the heat applied to fix the dye on thetextile material as this has been found to minimise the diffusion of thedye from printed to non-printed regions. As with the pre-treated textilematerial removal of water is preferably by heat, such as by exposure tohot air or to infrared or micro-wave radiation.

In stage (ii) of the present process, the printed textile material issubmitted to a short heat treatment, preferably after removal of waterby low-temperature drying, at a temperature from 100° C. to 200° C. byexposure to dry or steam heat for a period of up to 20 minutes. If asteam (wet) heat treatment is used, the printed material is preferablymaintained at 100-105° C. for from 5 to 15 minutes whereas if a dry heattreatment is employed the printed material is preferably maintained at140-160° C. for from 2 to 8 minutes.

After allowing the textile material to cool, unfixed dye and otheringredients of the pre-treatment and dye compositions may be removedfrom the textile material by a washing sequence, involving a series ofhot and cold washes in water and aqueous detergent solutions before thetextile material is dried.

According to further aspects of the present invention there are providedtextile materials, especially cellulosic textile materials, colouredwith any of the ink compositions according to the present invention orby means of the process according to the present invention.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1

Preparation of a Colorant of Formula (7) ##STR8## wherein: x is 1 and Ris H

and

x is 0 and R is C₂ H₄ NH₂

Step (a)

Preparation of CuPc [(SO₃ H)₂.1 (SO₂ NHC₂ H₄ Cl)₁.9 ]

Copper phthalocyanine (115.2 g) was added over 1/2 hour to well stirredchlorosulphonic acid (543 g) maintaining the temperature below 50° C.After a further 1/2 hour the mixture was heated to 140° C. and stirredat this temperature for 3 hours. It was then cooled to 40° C. and PCl₃(52.2 g) added over 1 hour, maintaining the temperature below 50° C. Themixture was then heated to 90° C. and stirred at this temperature for 2hours. The mixture was cooled and added to a stirred mixture of ice (700g), water (700 g), sodium chloride (100 g) and concentrated hydrochloricacid (40 cm³). The product was filtered and washed with hydrochloricacid (0.5N, 2 l) to give a paste.

2-chloroethylamine hydrochloride (46.4 g) was dissolved in water (1 l)and the solution stirred at 0° C. The abovementioned paste was added at0° C. and the pH adjusted to 7-8 using 2N NaOH solution. The mixture washeated to 40° C. and stirred at this temperature for 1/2 hour,maintaining the pH at 7-8 by addition of 2N NaOH solution. It was thencooled to 20° C. and stirred at 20° C. for 18 hours. The pH was adjustedto 1.5 using concentrated HCl and the precipitated product filtered-offand washed with 0.5N hydrochloric acid (1 l). The product was dried at60° C.

Analysis indicated the structure to be of Formula

    CuPc[(SO.sub.3 H).sub.2.1 (SO.sub.2 NHC.sub.2 H.sub.4 Cl).sub.1.9 ].

Step (b)

The product of step (a) (15 g) was dissolved in water (300 cm³) and thepH adjusted to 8.0 by addition of 2N sodium hydroxide solution.N-(2-aminoethyl)piperazine (20 g) was then added to the solution andstirred at 70-80° C. for 4 hours.

After cooling to 30° C., the pH was adjusted to 7.0 using concentratedhydrochloric acid. The product in free acid form was isolated byfiltration and washed with water.

The colorant in free acid form was charged into water (400 cm³) anddissolved by addition of 2M sodium hydroxide. The solution was dialysedto remove chloride ions, screened through a filter and evaporated todryness to give the sodium salt of the title mixture comprising a firstcompound wherein x is 1 and R is H, and a second compound wherein x is 0and R is C₂ H₄ NH₂.

When made into a 2% ink by dissolution in water/diethylene glycol(92.5/7.5) and printed onto plain paper using a thermal ink jet printer,the ink gave bright strong cyan coloured prints having high waterfastness and good light fastness.

EXAMPLE 2

Preparation of the Colorant of Formula (8): ##STR9## Step (a)

Example 1, step (a), was repeated except that 34.8 g of2-chloro-ethylamine hydrochloride was used instead of 46.4 g.

Step (b)

Example 1, step (b), was repeated except that the product of Example 2,step (a), was used in place of the product of Example 1, step (a). Theproduct in the free acid form was dissolved in water (400 cm³) byaddition of 2N NaOH solution to pH 10. The solution was dialysed,screened, evaporated and dried to give a mixture of two dyes of Formula(8) wherein in the first dye x is 1, R is H, y is 2.5 and z is 1.5, andin the second dye x is 0, R is C₂ H₄ NH₂, y is 2-5 and z is 1.5.

When made into an ink by dissolving 2 parts in water/2-pyrrolidone(90/10) and printed onto plain paper using a thermal ink jet printer thecolorant gave bright cyan prints having high water-fastness and goodlight fastness.

EXAMPLE 3

Step (a)

Example 1, step (a), was repeated except that 23.2 g of2-chloroethylamine hydrochloride was used in place of 46.4 g.

Step (b)

Example 1, step (b), was repeated except that in place of the productfrom Example 1, step (a), there was the product of Example 3, step (a)(15 g). The product (i.e. a mixture of two compounds of Formula (8)comprising a first compound wherein x is 1, R is H, y is 3.0 and z is1.0 and a second compound wherein x is 0, R is C₂ H₄ NH₂, y is 3.0 and zis 1.0) in the form of the sodium salt was dissolved in water (400 cm³)and dialysed, screened, evaporated and dried.

When made into an ink by dissolving 1 parts in water/2-pyrrolidone(90/10) and printed onto plain paper using thermal ink jet printer itgave bright cyan prints having high waterfastness and good lightfastness.

We claim:
 1. A compound which is effective for ink-jet printing,selected from the group consisting of compounds of Formula (1) and saltsthereof: ##STR10## in which: M is a metal or hydrogen;Pc is aphthalocyanine nucleus; each R¹ independently is H or optionallysubstituted alkyl, aryl or aralkyl; each L¹ independently is a divalentoptionally substituted alkylene, optionally substituted aralkylene oroptionally sulphonated arylene group; Z is an optionally substitutedpiperazinyl group; q is 1 or 2; x is from 1.5 to 3.0; y is from 1.0 to2.5; and (x+y) is from 2 to
 5. 2. A compound according to claim 1wherein Z is of the Formula (2): ##STR11## wherein: R² and R³ eachindependently is H or optionally substituted alkyl; andR⁴ is H,optionally substituted alkyl, aryl, aralkyl, acyl or ester group.
 3. Acompound according to claim 2 wherein R⁴ is an optionally substitutedC₁₋₄ -alkyl group.
 4. A compound of Formula (4) and salts thereof:##STR12## wherein: M is a metal or hydrogen;Pc is a phthalocyaninenucleus; each R¹ independently is H or optionally substituted, alkyl,aryl or aralkyl; R² and R³ each independently is H or optionallysubstituted alkyl; R⁴ is H, optionally substituted alkyl, aryl, aralkyl,acyl or ester group; R⁵ is H or optionally substituted alkyl; L² and L³each independently is an optionally substituted alkylene linking group;(x+y) is from 3 to 4; y is from 1 to 2.5; and b is 0 or
 1. 5. A compoundaccording to claim 2 or 4 wherein R⁴ is of Formula (3): ##STR13##wherein L¹ and each R¹ independently are as defined in claim
 1. 6. Acompound according to claim 4 wherein L² and L³ are C₂₋₄ -alkylene.
 7. Acompound according to any one of claims 2 to 6 wherein R² and R³ are Hor optionally substituted C₁₋₄ -alkyl.
 8. An ink comprising a compoundof Formula (1) or salt thereof and a medium: ##STR14## wherein: M is ametal or hydrogen;Pc is a phthalocyanine nucleus; each R¹ independentlyis H, optionally substituted alkyl, aryl or aralkyl; each L¹independently is a divalent optionally substituted alkylene, optionallysubstituted aralkylene or optionally sulphonated arylene group; Z is anoptionally substituted piperazinyl group; q is 1 or 2; x is from 1.5 to3.0; y is from 1.0 to 2.5; and (x+y) is from 2 to
 5. 9. An ink accordingto claim 8 wherein the medium is a liquid medium comprising water and awater-soluble organic solvent in a weight ratio of 99:1 to 1:99.
 10. Aprocess for printing a substrate with an ink using an ink jet printer,characterised in that the ink contains a compound of Formula (1) or saltthereof: ##STR15## wherein: M is a metal or hydrogen;Pc is aphthalocyanine nucleus; each R¹ independently is H, optionallysubstituted alkyl, aryl or aralkyl; each L¹ independently is a divalentoptionally substituted alkylene, optionally substituted aralkylene oroptionally sulphonated arylene group; Z is an optionally substitutedpiperazinyl group; q is 1 or 2; x is from 1.5 to 3.0; y is from 1.0 to2.5; and (x+y) is from 2 to
 5. 11. A paper or an overhead projectorslide printed with a compound of Formula (1) or salt thereof: ##STR16##wherein: M is a metal or hydrogen;Pc is a phthalocyanine nucleus; eachR¹ independently is H, optionally substituted alkyl, aryl or aralkyl;each L¹ independently is a divalent optionally substituted alkylene,optionally substituted aralkylene or optionally sulphonated arylenegroup; Z is an optionally substituted piperazinyl group; q is 1 or 2; xis from 1.5 to 3.0; y is from 1.0 to 2.5; and (x+y) is from 2 to
 5. 12.A process for the preparation of a compound of Formula (1): ##STR17##wherein: M is a metal or hydrogen;Pc is a phthalocyanine nucleus; eachR¹ independently is H, optionally substituted alkyl, aryl or aralkyl;each L¹ independently is a divalent optionally substituted alkylene,optionally substituted aralkylene or optionally sublphonated arylenegroup; Z is an optionally substituted piperazinyl group; q is 1 or 2; xis from 1.5 to 3.0; y is from 1.0 to 2.5; and (x+y) is from 2 to5comprising condensing a compound of Formula (5) ##STR18## In which G isa labile atom or group with a compound of Formula (6):

    H--Z                                                       Formula (6).


13. A process for the coloration of a textile material with an inkcomposition of claims 8 or 9 comprising a compound of Formula (1) whichcomprises the steps:i) applying to the textile material by ink jetprinting the ink composition; and ii) heating the textile material at atemperature from 50° C. to 250° C. to fix the dye on the material.